US5141705A - Austenitic stainless steel - Google Patents

Austenitic stainless steel Download PDF

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Publication number
US5141705A
US5141705A US07/637,144 US63714491A US5141705A US 5141705 A US5141705 A US 5141705A US 63714491 A US63714491 A US 63714491A US 5141705 A US5141705 A US 5141705A
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steel
max
consisting essentially
steel according
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US07/637,144
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English (en)
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Peter Stenvall
Mats Liljas
Bengt Wallen
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Outokumpu Stainless AB
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Avesta AB
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Assigned to AVESTAPOLARIT AB reassignment AVESTAPOLARIT AB CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: SHEFFIELD, AVESTA
Assigned to OUTOKUMPU STAINLESS AB reassignment OUTOKUMPU STAINLESS AB ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: AVESTA AKTIEBOLAG
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Classifications

    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28HEAT EXCHANGE IN GENERAL
    • F28FDETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F21/00Constructions of heat-exchange apparatus characterised by the selection of particular materials
    • F28F21/08Constructions of heat-exchange apparatus characterised by the selection of particular materials of metal
    • F28F21/081Heat exchange elements made from metals or metal alloys
    • F28F21/082Heat exchange elements made from metals or metal alloys from steel or ferrous alloys
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/58Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C30/00Alloys containing less than 50% by weight of each constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten

Definitions

  • This invention relates to an austenitic stainless steel having a high tensile strength, a high impact strength, a good weldability and high corrosion resistance, particularly a high resistance to pitting and crevice corrosion.
  • a way of improving the corrosion resistance of an austenitic stainless steel is to include nitrogen in the alloy composition.
  • Nitrogen has been utilized already in the above mentioned steel grade Avesta 254 SMO®, which contains a little more than 0.2% nitrogen. It is also known that the solubility of nitrogen can be further increased if the content of manganese or chromium is increased in the steel composition.
  • a means of reducing or avoiding the precipitation of inter-metallic phases is to alloy the steel with a high content of nitrogen. At the same time nitrogen may improve the pitting and crevice corrosion resistance of the steel.
  • chromium has a high affinity for nitrogen and it readily forms chromium nitrides when the contents of chromium and nitrogen are too high, which creates another problem in connection with these steels.
  • it is also necessary that the solubility to nitrogen in the molten phase of the steel is sufficiently high.
  • An improved nitrogen solubility in the molten phase may be achieved through increased contents of chromium and manganese.
  • the invention aims at providing a steel which advantageously can be used for example within the following fields:
  • the steel of the present invention therefore contains in weight-%:
  • the steel also may contain other elements in minor amounts, provided these elements do not impair the desired features of the steels which have been mentioned above.
  • the steel may contain boron in an amount up to 0.005% for the purpose of further increasing the hot workability of the steel.
  • the steel contains cerium, it normally also contains other rare earth metals, as these elements including cerium, normally are supplied in the form of mischmetal.
  • calcium, magnesium or aluminium may be added to the steel in amounts up to 0.01% of each element for different purposes.
  • Carbon is considered as a non-desired element in the steel of the invention, since carbon strongly reduces the solubility of nitrogen in the molten steel. Carbon also increases the tendency to precipitation of harmful chromium carbides. For these reasons carbon should not be present in the steel in amounts exceeding 0.08%, preferably not exceeding 0.05%, and suitably not exceeding 0.03%.
  • Silicon increases the tendency for precipitation of inter-metallic phases and reduces strongly the solubility of nitrogen in the molten steel. Silicon therefore may exist in an amount of max 1.0%, preferably max 0.7%, suitably max 0.5%.
  • Chromium is a very important element in the steel of the invention, as well as in all stainless steels. Chromium generally increases the corrosion resistance. It also increases the solubility of nitrogen in the molten steel more strongly than other elements in the steel. Chromium therefore is present in the steel in an amount of at least 19%.
  • Chromium however, particularly in combination with molybdenum and silicon, increases the susceptibility to precipitation of inter-metallic phases and in combination with nitrogen also the susceptibility to precipitation of nitrides. This may be critical for example in connection with welding and heat treatment. For this reason, the chromium content is limited to max 28%, preferably to max 27%, suitably to max 26%.
  • Molybdenum belongs to the most important elements in the steel of the invention due to its ability to strongly increase the corrosion resistance, particularly the resistance to pitting and crevice corrosion, at the same time as increasing the solubility of nitrogen in the molten steel. Also the tendency to precipitation of nitrides is diminished with increased content of molybdenum.
  • the steel therefore contains more than 7.0% molybdenum, preferably at least 7.2% Mo. It is true that problems may be expected in connection with hot rolling and cold rolling because of such a high content of molybdenum, but by a proper selection and adaptation of other alloying elements in the steel according to the invention it is possible to hot roll and to cold roll the steel successfully even with the high molybdenum contents which are typical for this steel.
  • molybdenum has a tendency to increase the susceptibility to precipitation of inter-metallic phases, e.g. in connection with welding and heat treatment.
  • the molybdenum content must not exceed 10%, preferably not exceed 9 %, and suitably not exceed 8.5%.
  • Nitrogen is a critical alloying element in the steel of the invention. Nitrogen very strongly increases the pitting and crevice corrosion resistance and it also strongly improves the mechanical strength of the steel, while at the same time maintaining good impact strength and deformability (shapeability). Nitrogen also is a cheap alloying element, as it can be added to a steel by adding air or nitrogen gas to the oxidizing gas in connection with the decarburization of the steel in the converter.
  • Nitrogen is also a strong austenite stabilizer, which affords several advantages.
  • some alloying elements may strongly segregate. This particularly concerns molybdenum, which exists in a high amount in the steel of the invention.
  • molybdenum In the inter-dendritic regions the molybdenum contents often may be so high that the risk for precipitation of inter-metallic phases is very great.
  • the austenite stability is so high that the inter-dendritic regions, in spite of the very high contents of molybdenum, will maintain their austenitic micro-structure.
  • the high austenite stability is advantageous, e.g. in connection with welding without consumable electrodes, since it will result in the material in the weld containing extremely low contents of secondary phases and consequently a higher ductility and corrosion resistance.
  • the inter-metallic phases which most commonly may occur in this type of steel are Laves's phase, sigma-phase, and chi-phase. All these phases have a very low or no solubility at all of nitrogen. Nitrogen for this reason may delay the precipitation of Laves's phase and also of sigma- and chi-phase. A higher content of nitrogen thus will increase the stability against precipitation of the said inter-metallic phases. For the above reasons, nitrogen is present in the steel in an amount of at least 0.4%, preferably at least 0.45% N.
  • the nitrogen content in the steel therefore must not exceed 0.7%, preferably not exceed 0.65%, and suitably not exceed 0.6% N.
  • Nickel is an austenite forming element and is added in order to establish the austenitic microstructure of the steel in combination with other austenite formers. An increased nickel content also counteracts the precipitation of inter-metallic phases. For these reasons, nickel is present in the steel in an amount of at least 17%, preferably at least 19%.
  • Nickel however, lowers the solubility of nitrogen in the molten state of the steel and it further increases the tendency to precipitation of carbides in the solid state. Furthermore, nickel is an expensive alloying element. Therefore the nickel content is restricted to max 25%, preferably max 24%, suitably max 23% Ni.
  • Manganese is added to the steel in order to improve the solubility of nitrogen in the steel in a manner known per se.
  • the research work in connection with the development of the steel has revealed that surprisingly low manganese contents are sufficient for making possible nitrogen contents exceeding 0.4%.
  • Manganese therefore is added to the steel in an amount of at least 0.5%, preferably at least 1.0%, and suitably at least 2.0% in order to increase the solubility of nitrogen in the molten state of the steel.
  • High contents of manganese cause problems during decarburization, since manganese like chromium reduces the carbon activity, so that the decarburization rate is slowed down.
  • Manganese furthermore has a high vapour pressure and a high affinity to oxygen which results in a considerable loss of manganese during decarburization if the initial content of manganese is high. It is further known that manganese may form sulphides which lowers the resistance to pitting and crevice corrosion.
  • the research work in connection with the development of the steel of the invention furthermore has shown that manganese dissolved in the austenite impairs the corrosion resistance even if manganese sulphides are not present.
  • the manganese content is restricted to max 6%, preferably to max 5%, suitably to max 4.5%, and most suitably to max 4.2%.
  • An optimal content of mangenese is appr. 3.5%.
  • Cerium may optionally be added to the steel, e.g. in the form of mischmetal, in order to increase the hot workability of the steel in a manner known per se.
  • cerium will form ceriumoxysulphides in the steel, which sulphides do not impair the corrosion resistance to the same degree as other sulphides, e.g. manganese sulphide. Cerium is therefore present in the steel in significant amounts up to max 0.2%, suitably max 0.1%. If cerium is added to the steel, the cerium content should be at least 0.03% Ce.
  • Sulphur must be kept at a very low level in the steel of the invention.
  • a low content of sulphur is important for the corrosion resistance as well as for the hot working features of the steel.
  • the content of sulphur therefore may be at most 0.01%, and, particularly for the purpose of achieving a good hot workability, the steel preferably should have a sulphur content less than 10 ppm ( ⁇ 0.001%) considering that an austentic stainless steel having as high contents of manganese and molbdenum as the steel of the invention normally is very difficult to hot work.
  • the steels also contained impurities and accessory elements in amounts which are normal for stainless austenitic steels, and for nickel base alloys, respectively.
  • the content of phosphorus was ⁇ 0.02%, and the content of sulphur was max 0.010%.
  • the sulphur content was ⁇ 10 ppm ( ⁇ 0.001%).
  • the steels No. 6 and No. 16 of the invention in comparison with conventional austenitic stainless steels have a high tensile strength and a good toughness in relation to its strength.
  • the structure stability of high alloyed austenitic steels usually is a measure of the ability of the steel of maintaining its austenitic structure when subjected to heat treatment in the temperature range 700°-1100° C. This feature is crucial for the weldability of the steel and for the possibility of heat treating the steel in large size dimensions. The greater tendency is to precipitation of secondary phases, the worse is the weldability as well as the possibility of heat treating large size (thick) goods.
  • the resistance to crevice corrosion and pitting were evaluated in 6% FeCl 3 -solution according to ASTM G-48.
  • a crevice former of multipel crevice type was used in the crevice corrosion test.
  • the critical temperature was recognized as the temperature where corrosion can be detected on the test surface after exposure to the FeCl 3 -solution for 24 hours.
  • the critical temperature was measured with an accuracy of ⁇ 2.5° C.
  • a high critical temperature always is advantageous, which means that the higher critical temperature is, the better is the corrosion resistance.
  • the commercially available materials of the nickel base alloys 17 and 18 in Table 2 were used during these tests.
  • the resistance against general corrosion in acids was evaluated by plotting the anodic polarization curves, and from these curves the passivation current density was calculated.
  • a low passivation current density implies that the alloy may be passivated more readily in the acid in question than an alloy having a higher passivation current density.
  • a low passivation current density is always advantageous, since the rate of corrosion of a passivated steel is much lower than the corrosion rate of a steel which has not been possible to be passivated.
  • the three acids which were used in the tests were 20% H 2 SO 4 at 75° C., 70% H 2 SO 4 at 50° C., and a phosphoric acid at 50° C.
  • the phosphoric acid had the following composition:
  • chromium and molybdenum are favourable for the corrosion resistance in most acids, and that manganese has very little effect. It is also known that chromium, and particularly molybdenum, has a favourable effect upon the resistance against pitting and crevice corrosion, but that alloys having very high contents of chromium and molybdenum may contain precipitations in the form of phases which are rich in chromium and molybdenum and that these phases may have an unfavourable influence upon the resistance against crevice corrosion and pitting. It is also known that manganese, through the formation of manganese sulphides, may have an unfavourable effect upon the resistance against crevice corrosion and pitting. For these reasons, the effect of chromium, molybdenum, and manganese has been studied only as far as crevice corrosion or pitting is concerned.
  • Steel No. 12 which has a high content of manganese, has a significantly lower critical temperature than steel No. 3.
  • the latter steel has a manganese content according to the invention but as far as other elements are concerned it has essentially the same alloy composition and essentially the same PRE-value as steel No. 12.
  • Steels having higher contents of copper than 0.49% thus have a lower critical temperature than steels having lower contents.
  • the impairment of the corrosion resistance is particularly great in the content range between 0.96 and 1.46% Cu.
  • Copper has no significant effect upon the passivation features in 20% H 2 SO 4 but has a favourable effect in 70% H 2 SO 4 . In the latter case, however, the major part of the improvement has been achieved already at 0.49% Cu. In phosphoric acid, the effect of copper is unfavourable.
  • the alloy according to the invention therefore has optimal corrosion features at a copper content of about 0.5% since:

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
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  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Heat Treatment Of Steel (AREA)
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  • Materials For Medical Uses (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
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  • Superconductors And Manufacturing Methods Therefor (AREA)
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US07/637,144 1990-01-15 1991-01-03 Austenitic stainless steel Expired - Lifetime US5141705A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE9000129 1990-01-15
SE9000129A SE465373B (sv) 1990-01-15 1990-01-15 Austenitiskt rostfritt staal

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US5141705A true US5141705A (en) 1992-08-25

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US (1) US5141705A (de)
EP (1) EP0438992B1 (de)
JP (1) JP3209433B2 (de)
KR (1) KR0167783B1 (de)
AT (1) ATE134391T1 (de)
AU (1) AU631280B2 (de)
CA (1) CA2033287C (de)
CZ (1) CZ7091A3 (de)
DE (1) DE69025468T2 (de)
DK (1) DK0438992T3 (de)
ES (1) ES2083444T3 (de)
FI (1) FI100341B (de)
HK (1) HK209996A (de)
HU (1) HU210752B (de)
NO (1) NO177604C (de)
PL (1) PL165989B1 (de)
SE (1) SE465373B (de)
ZA (1) ZA91151B (de)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5841046A (en) * 1996-05-30 1998-11-24 Crucible Materials Corporation High strength, corrosion resistant austenitic stainless steel and consolidated article
US6168755B1 (en) 1998-05-27 2001-01-02 The United States Of America As Represented By The Secretary Of Commerce High nitrogen stainless steel
WO2001068929A1 (en) * 2000-03-15 2001-09-20 Huntington Alloys Corporation Corrosion resistant austenitic alloy
US20030143105A1 (en) * 2001-11-22 2003-07-31 Babak Bahar Super-austenitic stainless steel
US20100126214A1 (en) * 2008-11-25 2010-05-27 Henri Paradowski Process for the production of a subcooled liquefied natural gas stream from a natural gas feed stream, and associated installation
US9803267B2 (en) 2011-05-26 2017-10-31 Upl, L.L.C. Austenitic stainless steel

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4110695A1 (de) * 1991-04-03 1992-10-08 Thyssen Schweisstechnik Stahl
FR2711674B1 (fr) * 1993-10-21 1996-01-12 Creusot Loire Acier inoxydable austénitique à hautes caractéristiques ayant une grande stabilité structurale et utilisations.
FR2705689B1 (fr) * 1993-05-28 1995-08-25 Creusot Loire Acier inoxydable austénitique à haute résistance à la corrosion par les milieux chlorurés et sulfuriques et utilisations.
DE4342188C2 (de) * 1993-12-10 1998-06-04 Bayer Ag Austenitische Legierungen und deren Verwendung
DE19631712C2 (de) * 1996-07-13 2001-08-02 Schmidt & Clemens Verwendung einer austenitischen Chrom-Nickel-Molybdän-Stahllegierung
KR20020008950A (ko) * 2000-07-21 2002-02-01 김성호 직조기용 종광 조성물
US6576068B2 (en) * 2001-04-24 2003-06-10 Ati Properties, Inc. Method of producing stainless steels having improved corrosion resistance
DE10215124A1 (de) * 2002-04-05 2003-10-16 Wme Ges Fuer Windkraftbetr Ene Verdampferrohr für eine Meerwasserentsalzungsanlage
SE528008C2 (sv) * 2004-12-28 2006-08-01 Outokumpu Stainless Ab Austenitiskt rostfritt stål och stålprodukt

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4086085A (en) * 1976-11-02 1978-04-25 Mcgurty James A Austenitic iron alloys

Family Cites Families (8)

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Publication number Priority date Publication date Assignee Title
SU190766A1 (de) * 1965-02-18 1966-12-29
SE411130C (sv) 1976-02-02 1985-09-09 Avesta Jernverks Ab Austenitiskt rostfritt stal med hog mo-halt
US4421557A (en) * 1980-07-21 1983-12-20 Colt Industries Operating Corp. Austenitic stainless steel
SE441455B (sv) * 1983-10-21 1985-10-07 Avesta Ab Stal av austenitisk typ
US4545826A (en) * 1984-06-29 1985-10-08 Allegheny Ludlum Steel Corporation Method for producing a weldable austenitic stainless steel in heavy sections
JPS6152351A (ja) * 1984-08-20 1986-03-15 Nippon Steel Corp 極低温耐力、靭性に優れた構造用オ−ステナイト系ステンレス鋼
JPS62182251A (ja) * 1986-02-06 1987-08-10 Nippon Kokan Kk <Nkk> 石油生産関連機器用耐食金属コ−テイング材料
JPH0694057B2 (ja) * 1987-12-12 1994-11-24 新日本製鐵株式會社 耐海水性に優れたオーステナイト系ステンレス鋼の製造方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4086085A (en) * 1976-11-02 1978-04-25 Mcgurty James A Austenitic iron alloys

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5841046A (en) * 1996-05-30 1998-11-24 Crucible Materials Corporation High strength, corrosion resistant austenitic stainless steel and consolidated article
US6168755B1 (en) 1998-05-27 2001-01-02 The United States Of America As Represented By The Secretary Of Commerce High nitrogen stainless steel
WO2001068929A1 (en) * 2000-03-15 2001-09-20 Huntington Alloys Corporation Corrosion resistant austenitic alloy
US20040120843A1 (en) * 2000-03-15 2004-06-24 Crum James R Corrosion resistant austenitic alloy
US6918967B2 (en) 2000-03-15 2005-07-19 Huntington Alloys Corporation Corrosion resistant austenitic alloy
US20030143105A1 (en) * 2001-11-22 2003-07-31 Babak Bahar Super-austenitic stainless steel
US7081173B2 (en) 2001-11-22 2006-07-25 Sandvik Intellectual Property Ab Super-austenitic stainless steel
US20100126214A1 (en) * 2008-11-25 2010-05-27 Henri Paradowski Process for the production of a subcooled liquefied natural gas stream from a natural gas feed stream, and associated installation
US9506690B2 (en) * 2008-11-25 2016-11-29 Technip France Process for the production of a subcooled liquefied natural gas stream from a natural gas feed stream, and associated installation
US9803267B2 (en) 2011-05-26 2017-10-31 Upl, L.L.C. Austenitic stainless steel

Also Published As

Publication number Publication date
SE9000129D0 (sv) 1990-01-15
NO910151D0 (no) 1991-01-14
PL288696A1 (en) 1991-07-29
KR910014530A (ko) 1991-08-31
HUT57282A (en) 1991-11-28
EP0438992B1 (de) 1996-02-21
JP3209433B2 (ja) 2001-09-17
JPH04214843A (ja) 1992-08-05
AU6867091A (en) 1991-07-18
SE465373B (sv) 1991-09-02
KR0167783B1 (ko) 1999-01-15
ATE134391T1 (de) 1996-03-15
NO177604C (no) 1995-10-18
EP0438992A1 (de) 1991-07-31
SE9000129A (de) 1991-07-16
FI906422A0 (fi) 1990-12-27
DE69025468D1 (de) 1996-03-28
HU210752B (en) 1995-07-28
ZA91151B (en) 1991-11-27
ES2083444T3 (es) 1996-04-16
DK0438992T3 (da) 1997-03-10
CA2033287C (en) 2001-08-21
CZ7091A3 (en) 1993-02-17
FI906422A (fi) 1991-07-16
NO910151L (no) 1991-07-16
HK209996A (en) 1996-12-06
DE69025468T2 (de) 1996-07-04
NO177604B (no) 1995-07-10
CA2033287A1 (en) 1991-07-16
HU910095D0 (en) 1991-08-28
PL165989B1 (pl) 1995-03-31
FI100341B (fi) 1997-11-14
AU631280B2 (en) 1992-11-19

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Owner name: AVESTA AKTIEBOLAG, BRUKSGATAN, S-774 01 AVESTA, SW

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:STENVALL, PETER;LILJAS, MATS;WALLEN, BENGT;REEL/FRAME:005560/0412

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